WO2017166914A1 - Initiateur d'atrp à trois bras présentant une structure conjuguée plate et procédé pour sa préparation - Google Patents

Initiateur d'atrp à trois bras présentant une structure conjuguée plate et procédé pour sa préparation Download PDF

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WO2017166914A1
WO2017166914A1 PCT/CN2017/072222 CN2017072222W WO2017166914A1 WO 2017166914 A1 WO2017166914 A1 WO 2017166914A1 CN 2017072222 W CN2017072222 W CN 2017072222W WO 2017166914 A1 WO2017166914 A1 WO 2017166914A1
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arm
solution
volume
white solid
reaction
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PCT/CN2017/072222
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English (en)
Chinese (zh)
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戴李宗
吴俣哲
袁丛辉
毛杰
李云同
许一婷
曾碧榕
罗伟昂
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厦门大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/42—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
    • C07C233/43—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

Definitions

  • the invention relates to a kind of polymerization reaction in polymer polymerization chemistry, in particular to a preparation method of a three-arm ATRP initiator having a planar conjugate structure.
  • Atom transfer radical polymerization is one of the most widely used methods for polymer synthesis.
  • the polymerization method has the dual characteristics of free radical polymerization and living polymerization, and has good universality, strong controllability and low cost.
  • the polymer synthesized by the method can not only achieve the expected polymerization molecular weight, but also achieve a narrow distribution range and high yield of the polymer, and thus is an effective tool for designing a novel macromolecular structure.
  • it has become common to synthesize multi-arm and star-shaped polymers by ATRP polymerization, and has gradually become a research hotspot in the field of polymer chemistry.
  • ATRP Atom transfer radical polymerization
  • the ATRP initiator can also be classified into a small molecule ATRP initiator and a macromolecular ATRP initiator depending on the molecular weight.
  • the small molecule initiators the three-arm small molecule ATRP initiator is characterized by a rich chemical structure and a complex spatial structure but also regular [Biomacromolecules-2015, 16, 723-732]. More importantly, small molecule initiators with highly planar conjugate properties and rich electrical properties are more conducive to the spatial arrangement and orientation of polymer chains, and are important tools for polymer structure design in polymer science.
  • a novel three-arm small molecule ATRP initiator was synthesized by nucleophilic substitution reaction of 1,3,5-tris(4-aminophenyl)benzene and bromoisobutyryl bromide under the catalysis of triethylamine.
  • the initiator has the characteristics of highly planar conjugate properties and rich electrical properties as well as efficient chain transfer. Its Learning structure:
  • the optimal reaction system and post-treatment method suitable for the initiator were screened out.
  • the three-arm amphiphilic polymer was synthesized by ATRP polymerization using the initiator to carry out corresponding self-assembly research.
  • the invention aims to provide a preparation method of a three-arm ATRP initiator having a planar conjugate structure and application thereof
  • the macromolecular chain transfer agent 0.3 to 1 part by volume of tris(2-dimethylaminoethyl)amine, 0.1 to 1 part of cuprous bromide, and 1 to 3 parts by volume of t-butyl acrylate are dissolved in the DMF solution. After degassing by continuous freeze-thaw three times, it was argon-protected and placed in an oil bath at 90 ° C for 24 hours. After the reaction was completed, the copper salt was removed through a neutral alumina column. Further, precipitation was carried out by using a mixed solution of methanol and water to obtain a block polymer white solid. The block polymer white solid and 3 to 5 parts by volume of trifluoroacetic acid were dissolved in dichloromethane. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, the mixture was precipitated with a mixed solution of methanol and water to a three-armed amphiphilic block polymer in the form of a white solid.
  • the structure of the three-arm initiator in the present invention is ingeniously designed, the synthesis step is simple, and the yield is high.
  • the initiator has a high degree of planar conjugation and power enrichment as well as efficient initiation activity and chain transfer.
  • the optimum reaction system and post-treatment method of the three-arm ATRP initiator are screened in the present invention.
  • the reaction system has good universality, strong operability, simple post-treatment process and little environmental pollution, and can be applied to ATRP controlled polymerization of various monomers.
  • the polymer synthesized by the initiator in the present invention can be self-assembled in a solvent, and the self-assembly behavior of the polymer can be artificially controlled and further researched and applied by controlling the degree of polymerization.
  • Figure 1 is a nuclear magnetic resonance spectrum of a three-arm ATRP initiator with a nuclear magnetic spectroscopy: 9.90 (3H, s), 7.90 to 7.81 (15H, m), 2.04 (18H, s);
  • Figure 2 is a GPC spectrum of a three-armed amphiphilic ATRP polymer
  • a macromolecular chain transfer agent 0.3 ml of tris(2-dimethylaminoethyl)amine, 0.1 cuprous bromide, and 1 t-butyl acrylate were dissolved in a DMF solution. After degassing by continuous freeze-thaw three times, it was argon-protected and placed in an oil bath at 90 ° C for 24 hours. After the reaction was completed, the copper salt was removed through a neutral alumina column. Further, precipitation was carried out by using a mixed solution of methanol and water to obtain a block polymer white solid. The block polymer white solid and 3 ml of trifluoroacetic acid were dissolved in dichloromethane. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, precipitation was carried out by using a mixed solution of methanol and water to obtain a three-armed amphiphilic block polymer as a white solid.
  • a macromolecular chain transfer agent 0.5 ml of tris(2-dimethylaminoethyl)amine, 0.2 cuprous bromide, and t-butyl 2 acrylate were dissolved in a DMF solution. After degassing by continuous freeze-thaw three times, it was argon-protected and placed in an oil bath at 90 ° C for 24 hours. After the reaction was completed, the copper salt was removed through a neutral alumina column. Further, precipitation was carried out by using a mixed solution of methanol and water to obtain a block polymer white solid. The block polymer white solid and 5 ml of trifluoroacetic acid were dissolved in dichloromethane. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, precipitation was carried out by using a mixed solution of methanol and water to obtain a three-armed amphiphilic block polymer as a white solid.
  • the macromolecular chain transfer agent 0.5 ml of tris(2-dimethylaminoethyl)amine, 0.6 cuprous bromide, and tert-butyl triacrylate were dissolved in the DMF solution. After degassing by continuous freeze-thaw three times, it was argon-protected and placed in an oil bath at 90 ° C for 24 hours. After the reaction was completed, the copper salt was removed through a neutral alumina column. Further, precipitation was carried out by using a mixed solution of methanol and water to obtain a block polymer white solid. The block polymer white solid and 5 ml of trifluoroacetic acid were dissolved in dichloromethane. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, precipitation was carried out by using a mixed solution of methanol and water to obtain a three-armed amphiphilic block polymer as a white solid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Polymerization Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un initiateur de polymérisation radicalaire par transfert d'atomes (ATRP) à trois bras présentant une structure conjuguée plate. Premièrement, on fait réagir le 1,3,5-tris(4-aminophényl)-benzène dans une réaction de substitution nucléophile avec du bromure de bromo-isobutyryle sous catalyse par la triéthylamine pour préparer un initiateur d'ATRP à trois bras hautement efficace présentant des caractéristiques d'une conjugaison plate étendue et de richesse en électrons. Deuxièmement, un système de réaction optimal et un procédé de post-traitement approprié pour l'initiateur sont sélectionnés. Une étude d'autoassemblage correspondant à un polymère macromoléculaire amphiphile à trois bras préparé par polymérisation ATRP à l'aide de l'initiateur est réalisée. L'initiateur d'ATRP à trois bras de la présente invention non seulement satisfait au besoin d'un initiateur d'ATRP conjugué plan, aromatique riche en électrons, mais convient également pour la polymérisation de divers types de monomères, présentant ainsi un bon potentiel d'application.
PCT/CN2017/072222 2016-04-01 2017-01-23 Initiateur d'atrp à trois bras présentant une structure conjuguée plate et procédé pour sa préparation WO2017166914A1 (fr)

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CN105622788B (zh) * 2016-04-01 2017-10-27 厦门大学 具有平面共轭结构的三臂atrp引发剂及其制备与应用
CN106748869A (zh) * 2016-11-23 2017-05-31 厦门大学 一种三官能度化合物及其制备方法和应用
CN107628966B (zh) * 2017-10-13 2019-12-13 厦门大学 一种具有光响应性的三臂链转移剂的制备方法
CN115745747B (zh) * 2022-11-02 2024-01-19 香港中文大学（深圳） 三臂星型有机自旋分子引发剂、均聚物、嵌段共聚物及其制备方法和聚合物薄膜

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CN103172776A (zh) * 2013-04-08 2013-06-26 中国农业大学 荧光星形聚合物、其制备方法及应用
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